JP2510615B2 - Breathable waterproof layer - Google Patents

Description

The present invention relates to a waterproof layer for a roof of a building. More specifically, the present invention relates to a breathable waterproof layer having a strong adhesive force with a waterproof underlayer and having a breathable buffer layer, which has excellent followability of underlayer cracks and does not change in shape such as swelling.

[Conventional technology and its problems]

Conventionally, waterproofing of flat roofs of buildings such as reinforced concrete condominiums and public apartments has been carried out, and various waterproofing works such as asphalt waterproofing, mortar waterproofing, sheet waterproofing, and coating film waterproofing have been performed in order to prevent water leakage. Particularly in recent years, with the progress of construction methods, waterproofing of coating film has shown remarkable growth. This is extremely easy to work on complicated surfaces, and has a very good workability such as a seamless waterproof layer. Particularly in recent years, mainly in large cities, roof construction of schools, buildings, condominiums, etc. is often used, and sports facilities such as tennis and volleyball and playgrounds are often used on top of them. A polyurethane-based waterproof material is mainly used as a material having waterproof performance and physical properties suitable for these purposes.

In general, urethane-based waterproof film is solvent-free, so a thick film can be obtained with a single application. It is necessary to apply even under low temperature in winter. The obtained film has excellent water resistance.
It has excellent features such as high impact resilience, good walking feeling, and strong wear resistance.

However, on the other hand, if the substrate is cracked due to uneven adhesion or air bubbles depending on the dryness and smoothness of the substrate, zero span tension is applied to that part, causing creep rupture and water leakage trouble. If it is wet, there is a defect that blisters easily occur due to peeling of the adhesive surface after the construction.

In order to solve these drawbacks, a buffer layer is provided between the waterproof underlayer and the urethane-based coating layer, and the underlayer and the buffer layer are bonded with an adhesive, or a hole is formed in the buffer layer to form a waterproof coating layer. Although it is applied to the groundwork, in the case of the former, the ventilation effect of the buffer layer is insufficient, and in the case of the latter, on the contrary, the adhesive force is small and it rises. When unsaturated polyester resin waterproof material is used instead of urethane waterproof material, the curing shrinkage of unsaturated polyester resin waterproof material moves the buffer layer attached to the base to separate the waterproof layer from the base. The movement of the movement is not transmitted to the waterproof layer, and the buffering effect that the moisture from the base is not vented through the buffering layer to cause "blisters" is reduced, or the portion that contacts the holes of the buffering layer is included in the buffering layer. Oxygen in the air interferes with curing, resulting in an uncured state, the adhesive strength between the base and the waterproof layer is significantly reduced, the waterproof layer is poorly packed, and it becomes impossible to dig into negative pressure due to wind, etc. In the worst case, there is a drawback that peeling occurs from the end of the waterproof layer.

[Means for solving problems]

As a result of various studies to solve these problems, the present inventor found that the surface of the cured product does not become uncured by combining an isocyanate compound with an unsaturated polyester resin having excellent water resistance, The present invention has been reached.

That is, the present invention comprises a. Waterproof underlayer, b. Intermediate layer which is a breathable buffer layer with holes, c. Upper layer which is a waterproof layer, and b has a layer for preventing permeation of the resin liquid on the upper surface. Where c is adhered to a at the perforated portion, and c is a mixture of 0.5 to 10 parts by weight of an isocyanate compound with 100 parts by weight of an unsaturated polyester resin and cured. It is a breathable waterproof layer that does not cause blistering even if the base is wet, and does not place a heavy burden on the waterproof layer against zero span tension or repeated fatigue that occurs when the base cracks. In addition, the existing asphalt exposure and waterproofing repair work will not reduce the adhesive strength and prevent bleeding due to the asphalt pool.

As the underlayer of a used in the present invention, inorganic materials such as holding concrete, mortar, precast concrete and lightweight concrete for molten asphalt waterproof layer, sheet waterproof layer such as rubber sheet, vinyl chloride sheet, polyurethane,
Examples include organic materials such as acrylic rubber such as waterproof film for coating film, which can be used not only for new installations but also for repairs and repairs.

The perforated breathable buffer layer of b used in the present invention preferably has a layer for preventing the permeation of the resin liquid on the upper surface, and for example, perforated nylon, vinylon, polyester or the like having one side thermally fused The non-woven fabric may be a non-woven fabric, or a non-woven fabric obtained by laminating a film or sheet on one surface with heat or an adhesive, and opening the non-woven fabric. Its thickness is usually 1 to 10 mm. The diameter of the pores is usually 1 to 30 mm, and the pores may have a uniform size or may have a non-uniform size, but it is preferable that the pores are dispersed over the entire surface. If it is localized, the adhesive force between the waterproof layer and the underlayer will not be uniform, and wrinkles may occur due to expansion and contraction of the waterproof layer due to temperature changes.

The unsaturated polyester resin used in the present invention is a mixture of unsaturated polyester and unsaturated monomer.

Unsaturated polyesters can be obtained by condensation and addition reactions of alcohol compounds and carboxylic acid compounds (including acid anhydrides and alkyl ester compounds of carboxylic acids). Among them, especially derived from diol components and dicarboxylic acid components. Those are preferable. More preferably, the unsaturated polyester has 1 to 25 mol% of the unsaturated acid with respect to the total amount of the dicarboxylic acid, and does not contain an unsaturated bond in the chain of the unsaturated polyester, or even if it contains the unsaturated bond to the total dicarboxylic acid. The ratio of unsaturated carboxylic acid is preferably 8.0 mol% or less. If the amount of unsaturated acid at the terminal is more than 25 mol%, the elongation of the cured product will be significantly reduced, the rubber elasticity will be impaired and it will become hard, making it impossible to follow the cracks in the base. If the amount of unsaturated acid at the terminal is less than 1 mol%, the number of cross-linking points in the unsaturated polyester resin will be small, gelation will be poor, and stickiness will occur forever and stain easily. Moreover, the physical performance of the coating film is not good. Also,
If the amount of unsaturated bonds in the chain is more than 8.0 mol%, the coating film becomes hard at low temperature and loses elongation and becomes brittle.

The diol component consists mainly of dihydroxy compounds,
Partially, for example, it may contain up to 20 mol% of a polyhydroxy compound such as a triol compound. In this case, it is necessary to adjust the average number of functional groups to be equivalent to the dihydroxy compound by blending, for example, a monohydroxy compound. Appropriate. Examples of the dihydroxy compound include aliphatic dialcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3 butanediol, 1,4 butanediol and neopentyl glycol, and alicyclic dihydroxy compounds such as 4,4-dihydroxydicyclohexylpropane. Examples thereof include aromatic dihydroxy compounds such as alkylene oxide adducts such as ethylene oxide or propylene oxide of bisphenol A.

Examples of polyhydroxy compounds include trimethylolpropane, glycerin, and pentaerythritol.

Examples of the monohydroxy compound include aliphatic alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, iso-butyl alcohol and nonyl alcohol, alicyclic monoalcohols such as hexanol and aromatic monoalcohols such as benzyl alcohol. Is mentioned.

Carboxylic acid compounds include adipic acid, sebacic acid,
Phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 3,6-endomethylenetetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
One or two saturated acids such as tetrachlor phthalic anhydride and unsaturated acids such as maleic anhydride, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, chlorinated maleic acid, acrylic acid and methacrylic acid. Used more than one species.

Unsaturated monomers are used for facilitating painting and construction, and for accelerating the polymerization reaction and polymerizing. The usage amount is workability, flexibility, hardness, weather resistance, solvent resistance. The range is 10 to 70% by weight depending on the intended use such as drying property.

Examples of unsaturated monomers include styrene, vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (methyl)
There are glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc., and they are used alone or in combination of two or more.

The amount of the unsaturated monomer used is in the range of 10 to 70% by weight depending on the intended use such as workability, flexibility, hardness, weather resistance, solvent resistance and drying property.

The polyester resin requires a polymer compound, a plasticizer, a curing catalyst (a crosslinking initiator, a crosslinking initiation auxiliary agent, etc.), and a filler in order to adjust the viscosity, modify the physical properties of the cured product, and improve the curing speed. It is possible to add. Polymers that can be used are those that have been mixed in order to reduce the manufacturing cost and improve the coating performance or coating performance when used as a coating material, such as acrylic resin,
Examples thereof include polyester resin, polyurethane resin, styrene-allyl alcohol copolymer, polyethylene and wax. Examples of the plasticizer include dioctyl phthalate, dibutyl phthalate, butyl phthalyl butyl glycolate, tricresyl phosphate, chlorinated paraffin and the like. In addition, bottom residues during petroleum refining such as asphalt and clean products such as coal tar can be added in order to improve coating film performance and improve compatibility with the base.

The curing catalyst added as needed can be appropriately selected depending on the curing method. When high energy such as electron beam is used, a polymerization initiator is not particularly required, but if light or ultraviolet rays are used, a well-known photosensitizer is required as a polymerization initiator, and if heat energy or far infrared rays are used. Suitable polymerization initiators are peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, ditertiary butyl peroxide, lauroyl peroxide, cumene hydroperoxide, and metal soaps such as cobalt naphthenate and dimethyl as polymerization initiators. Tertiary amines such as aniline, alcoholates such as sodium methylate, lauryl mercaptan, N-ethyl metatoluidine and the like are suitable.

In addition to these components, various substances can be added for the purpose of improving the performance of the cured product. These additives include pigments such as titanium white, carbon black, red iron oxide, etc., solvents such as benzene, toluene, methyl ethyl ketone, mineral toprite, polyethylene, polypropylene, nylon, calcium carbonate, magnesium carbonate, presence / absence of sulfuric acid, calcium sulfate. Add fillers such as alumina, clay, kaolin, talc, diatomaceous earth, silica gel, mica powder, glass fiber powder, asbestos powder, silica stone powder, bentonite, colloidal silicic acid, castor oil derivatives and other thixotropic agents. Can be done.

The isocyanate compound used in the present invention is a compound containing at least one or more active isocyanate groups in one molecule. Examples thereof include aliphatic isocyanates such as trimethylhexamethylene diisocyanate, isophorone diisocyanate, and alicyclic isocyanates such as hydrogenated MDI, alone or in a mixture.

The amount of the active isocyanate compound added to 100 parts by weight of the unsaturated polyester resin is 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight. If the amount is less than 0.5 part by weight, the reaction of the surface of the unsaturated polyester resin cured product is not sufficient, and the uncured portion causes stickiness, and the adhesive force between the base and the waterproof layer is not improved. On the other hand, if it exceeds 10 parts by weight, it reacts with water in the unsaturated polyester resin waterproof material to generate carbon dioxide gas, which causes foaming of the waterproof layer or pinholes, resulting in a marked deterioration of the waterproof function.

In order to form the waterproof layer of the present invention, a perforated breathable buffer layer is spread on the waterproof underlayer so that the layer for preventing the permeation of the resin liquid is on the upper surface so as to be uniform. At that time, an adhesive may be used so that the buffer layer can be fixed between the base and the buffer layer, but if a large amount of adhesive is used, the buffer layer is clogged, and the movement of air and water vapor generated from the base is prevented. Since it may be stopped, usually 100 ~
400 grams, preferably 200-400 grams. Then, the mixture of the unsaturated polyester resin and the isocyanate compound may be applied and cured by a general application means such as a rubber spatula, a brush, a roller or other construction equipment, or a spray or other mechanical coating. The thickness of the waterproof layer is usually 0.5-3 mm.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following, parts are based on weight, unless otherwise specified. In addition,
The test results of Examples and Comparative Examples are summarized in Table 1.

The outline of the test method performed in this example is described below.

(Breathability test) A cushioning material was placed on a precast concrete plate, and a sample (width 40 cm, length 130 cm) was applied according to the specifications of the example and comparative example. An air pressure of 0.1 kgf / cm ² was applied to one end between the two (10 cm) points (interval 100 cm), and the amount of air discharged from the other end was measured.

(Negative pressure resistance) A transparent plastic funnel (30 cm in diameter) is placed on the test piece prepared in the same manner as the breathability test, the periphery is sealed, and the pressure is reduced by 100 cm with a pressure reducer and held for 1 hour. Then, the state of the waterproof layer was observed while maintaining the negative pressure.

(Adhesiveness test) A test piece prepared in the same manner as the breathability test was cut into a piece having a width of 2.5 cm, the tip portion was gripped with a jig and slowly pulled from an angle of 150 ° to measure the adhesive strength.

(Permeability test) In accordance with JIS A-6910, a glass funnel (diameter 7.5 cm) is laid down on the specimen, a measuring pipette is set up with a rubber tube at the tip of the funnel, the periphery is sealed with a sealing material, and water is removed. The water permeability was measured from the height of the water head 24 hours after the water was sealed up to a height of 25 cm.

Example 1 1,4-Butanediol was added to a four-necked flask equipped with a stirrer, a thermometer, a condenser equipped with a condenser, and a nitrogen inlet tube.
After charging 6.3 parts and 6.7 parts of citraconic anhydride and reacting at a temperature of 120 ° C, 131.4 parts of adipic acid and 7.0 parts of fumaric acid were added, and an esterification reaction was carried out at 210 ° C in a nitrogen stream, followed by p-tersia. Ributylcatechol 0.05 parts, melting point 56-
A pale yellow liquid was obtained by dissolving 2 parts of wax at 58 ° C. in 205 parts of dissolved styrene.

100 parts of this pale yellow liquid, titanium oxide JR701 as a pigment
10 parts (made by Teikoku Kako) and 10 parts 3S talc (made by Shiraishi Calcium) as a filler are uniformly mixed and dispersed at room temperature under high speed stirring. Immediately before use, 1.5 parts of benzyl peroxide as an initiator and as a starting aid. 0.5 parts of aniline and 3 parts of liquid diphenylmethane diisocyanate were blended to obtain an unsaturated polyester waterproof material.

A urethane primer is applied on a precast concrete board so that the weight per square meter is 0.2 kg, and a perforated single-sided heat-bonded non-woven fabric (trade name: punch sheet ... The hole is filled with a waterproof material sufficiently, and 2.
After applying it to 0 kg, let it cure at room temperature for 1 week,
A breathability test, a negative pressure resistance test, an adhesion test, and a water permeability test were performed.

Example-2 In exactly the same manner as in Example-1, except that 5 parts of a hexamethylene diisocyanate-based adduct product (trade name; Coronate HL ... made by Nippon Polyurethane Co., Ltd.) was used in place of the liquid diphenylmethane diisocyanate in Example-1. A waterproof layer was prepared by using the method, and a breathability test, a negative pressure resistance test, an adhesion test, and a water permeability test were performed.

Example 3 Diethylene glycol was placed in a four-necked flask equipped with a stirrer, a thermometer, a condenser equipped with a condenser, and a nitrogen inlet tube.
After charging 113.4 parts and 3.9 parts of maleic anhydride and reacting at a temperature of 120 ° C, 173.7 parts of sebacic acid and 13.0 parts of mesaconic acid were added, and after esterification reaction at 210 ° C in a nitrogen stream, hydroquinone 0.05 parts , A wax having a melting point of 56 to 58 ° C. was dissolved in 268 parts of styrene in which 2 parts of wax was dissolved to obtain a pale yellow liquid. To 100 parts of this pale yellow liquid, 10 parts of titanium oxide JR701 (manufactured by Teikoku Chemical Co., Ltd.) as a pigment and 10 parts of 3S talc (manufactured by Shiraishi calcium) as a filler are uniformly mixed and dispersed for high-speed stirring at room temperature, and further immediately before use. 1.5 parts of benzyl peroxide as an initiator, 0.5 part of aniline as an initiation aid,
Further, 3 parts of liquid diphenylmethane diisocyanate was blended to obtain an unsaturated polyester waterproof material.

A waterproof layer was prepared in the same manner as in Example 1 except that this waterproof material was used, and a breathability test, a negative pressure resistance test, an adhesion test, and a water permeability test were performed.

Comparative Example-1 A waterproof layer was prepared in the same manner as in Example-1, except that the liquid diphenylmethane diisocyanate was changed to 0.1 part in Example-1, and a breathability test, a negative pressure resistance test, an adhesion test, and a water permeability were conducted. A sex test was conducted.

Comparative Example-2 A waterproof layer was prepared in the same manner as in Example-1 except that the liquid diphenylmethane diisocyanate was changed to 15 parts in Example-1, and a breathability test, a negative pressure resistance test, an adhesion test, A water permeability test was conducted.

Comparative Example-3 Instead of the perforated single-sided heat-bonded nonwoven fabric (punched sheet) in Example-1, a polyester non-woven fabric having a unit weight of 80 g / m ² (trade name; MT FLEKEEP ... Mitsui Toatsu) A waterproof layer was prepared in the same manner as in Example 1 except that (Chemical) was used, and a breathability test, a negative pressure resistance test, an adhesion test, and a water permeability test were performed.

[Effects of the invention] As is clear from the examples, only the unsaturated polyester resin waterproof material causes uncured phenomenon due to the effect of air in the cushioning material at the portion in contact with the cushioning material, resulting in stickiness and curing. Since the strength of the object is weakened, the adhesive strength to the substrate is significantly reduced. On the other hand, the waterproof layer of the present invention does not have such drawbacks and is extremely suitable as a waterproof layer for a roof.

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Claims (1)

(57) [Claims] 1. A waterproof underlayer, b. An intermediate layer that is a perforated air-permeable buffer layer, c. An upper layer that is a waterproof layer, and b has a layer that prevents permeation of the resin liquid on the upper surface. Where c is adhered to a at the perforated portion, and c is a mixture of 0.5 to 10 parts by weight of an isocyanate compound with 100 parts by weight of an unsaturated polyester resin and cured. Breathable waterproof layer.